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Innovation in Industrial Technologies: the case of batteries

Innovation in Industrial Technologies: the case of batteries. Anne de Guibert Aarhus 20 June 2012. Energy availability in a moving and clean world. Energy storage has a key role to play in our world societal evolution

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Innovation in Industrial Technologies: the case of batteries

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  1. Innovation in Industrial Technologies: the case of batteries Anne de Guibert Aarhus 20 June 2012

  2. Energy availability in a moving and clean world • Energy storage has a key role to play in our world societal evolution • Each new generation of nomad communication devices (phone, computer, tablets…) needs batteries with increased energy density storage • More electric vehicles (cars, boats, planes…) will be at least a partial solution to progressive oil scarcity as well as CO2 or particles reduction (societal demand). They require top-performing batteries with long life, low cost, high energy/power, good safety • Weak networks and integration of intermittent renewable energy on the grid beyond 20-25 % will need energy storage. Here also batteries will play their part, especially for high power demands or small/mid size residential systems 2

  3. The various storage possibilities: energy and power EC Document “Energy Storage : A key technology for decentralized power, power quality and clean transport” - 2001

  4. Saft is recognised worldwide as the leading designer, developer and manufacturer of nickel-based battery solutions for the industrial, transport and professional electronic sectors. Saft. A world leader in high technology batteries The Group is the world’s leading designer, developer and manufacturer of high-performance primary lithium and rechargeable lithium-ion (Li-ion) battery systems for both civil and military markets. World leader in lithium-ion satellite batteries, Saft is also delivering its Li-ion technology to new applications in clean vehicles and energy storage systems. The Saft Group in 2011

  5. Content Present choices and deployment status The 3 steps of improvement roadmap 2014-2020 Towards industrial cells at 250 Wh/kg ? Beyond Li-ion : Li-sulfur, Li-air, sodium or magnesium batteries ?? Materials: the heart of batteries 1 2 3 4 5 6

  6. Batteries for more electric, cleaner vehicles • Batteries are designed for four levels of applications and specifications: • Stop-and-start : lead-acid batteries, improved from starter batteries + possibly supercapacitors , Li-ion. Usable energy <500 Wh • Hybrids with the emblematic Toyota Prius (NiMH batteries). More recent hybrid cars use Li-ion technology. Available energy < 1.5 kWh : small battery, high power • Plug-in : 5-10 kWh • Pure electric : 20 kWh minimum, 30 or more preferred. Lithium technology 4

  7. Lithium-ion hybrid vehicles application • From120V to 400 V ; 1-2 kWh • NCA cathode material for the best power and life • in application since 2009 in Germany and USA Mercedes S400 Hybrid with Saft Li-ion PROPRIETE SAFT

  8. Pure EV Nissan Leaf car of the year 2011 Battery technical characteristics: . Laminated Li-ion battery 24 kWh made of 48 modules of 4 cells (2x2) . Power > 90 kW . Energy density 140 Wh/kg . Autonomy 160 km . Life: 5 years ; e.o.l. at 80% initial capacity . Under the floor and seats of the vehicle Batteries built by AESC (jv Nissan-Nec) Sales began in April 2010 Charge: . duration < 8 hours on 220 V home plug . fast charge: 80% capacity in 30 min 9

  9. Bolloré Blue car • Innovation in utilization (Autolib) • Use metallic lithium as negative electrode active material (alone against all other manufacturers) Technical characteristics given by the manufacturer: . 30 kWh battery . Power 60 kW . Specific energy 140 Wh/kg . Autonomy 250 km . Life: 10 years/ 1200 cycles . Operation at 60-100°C ( Li-polymer technology) 10

  10. NiMH: a powerful battery for heavy duty • Saft Ni-MH 750 V 30 kWh 200 kW battery: system mass: 1 t for tram open battery system open battery system • Alkaline battery with metallic rare earth alloy as negative active material cell/module

  11. Batteries for stationary applications • Up to now, 90 % of batteries for storage application utilized lead-acid technology. The 10 % remaining are NiCd used for severe conditions applications • New applications (smart grids, association with renewable energies) are lithium-ion oriented: long life, absence of maintenance, high power for frequency control are determining qualities • High specific energy is not as important as for mobility. Life and cost are key issues, power can be.

  12. Li-Ion for standby energy delivery • Energy systems • 600 Wh • 1U- 19 ’’  • 300 Wh • 1U- 1/2 19 ’’  • 48 V • 2 300 Wh • 102 Wh/kg • 3U- 19 ’’ • accu VL45E • 150 Wh/kg IntensiumFlex • Tension Maximum : 750V DC • Courant Maximum: 300A, 300 sec

  13. Evolion, the last born standby energy storage module • Module of 14 cells – 80 Ah . Modular complete systems with charger and electronics in standard containers . Energy up to several MWh 13

  14. From very high power to very high energy Ultra-high power (VLU) Very-high power Li-ion (VLV) High Power Li-ion (VLP) Super capacitor Medium Power Li-ion (VLM) High energy Li-ion (VLE) AgO-Zn Ni-Cd Ni-MH Specific energy at cell scale Standard Lead-Acid CONFIDENTIEL SAFT

  15. Versatility of Li-ion subsystems: innovation in materials is essential C/LiCoO2 C/NCA C/NMC(s) Li-ion chemistries C/LiFePO4 and other LiMPO4 C/LMO new generations for >0 & <0 C/LiFePO4 & LiMPO4 C/LiFePO4 and other LiMPO4 Li4Ti5O12/NMC

  16. Strengths : The best specific energy (up to 230 Wh/kg in energy cell for consumer application) Good volumetric energy Excellent cyclability Good calendar life Very high power possible (up to 12 kW/kg in pulses) Excellent energetic efficiency Numerous subsystems: possible optimization for different specifications Weaknesses : Global cost of technology Complex electronic management compulsory Safety of large cells and batteries in abusive conditions needs further improvement High power chargeability to improve, especially at low temperature (ability to charge and discharge at the same rate) The great majority of emerging applications use Li-ion batteries: strengths & weaknesses of the technology

  17. Expressed needs: guidelines for the roadmap • Higher specific energy and energy density for pure EVs and plug-in • Specific power increase for hybrid vehicles without life decrease; ability to charge and discharge at the same high rate (HEV & standby frequency regulation) • Reliability & safety level EUCAR IV minimum • Life 8 years for cars (end of life -20% capacity), more for stationary • Cost decrease for all applications 17

  18. Bases of roadmap for batteries improvement • At short/mid term, to take the best from Li-ion recent technical solutions for incremental improvements: • To increase energy or specific power available • To optimize choices for applications (global demands often contradictory) • To simplify/standardize systems for cost reduction while keeping the same safety level • In parallel, to study the feasibility for industrial large batteries or solutions emerging soon in portable cells (ex. Si et composites Si-C) or for known materials in development (‘NMC Li rich’) • Increase networking with Universities on breakthrough innovations for the following generations and the ‘after Li-ion’ 18

  19. Step 1: implementation 2-3 years ahead 19

  20. Example: draw more from positive active materials (EV) • Except for LiFePO4 where nothing more can be expected, charge of cells is voltage limited (NMC, NCA, LCO) though the material is not fully charged: • To get a sufficient calendar life by limiting electrolyte decomposition and avoid structural changes at the surface of materials • To Improve safety • To use less materials NCA, NMC additional capacity at high voltage Possibility to recover 10-15 % more capacity LiFePO4 : no additional capacity 20

  21. Example: draw more from positive active materials (VE) • To increase available energy, the solution of voltage increase has begun to be implemented in portable cells with limited life. Industrial applications need much longer life and safe big batteries which are developed : • Using surface protection (nano coatings) for interface stabilization • Safety being reinforced by other methods (HRL) • With necessary research on electrolytes and additives • Optimization for applications can be done by different choices of materials and their mixes to combine positive effects and decrease drawbacks: • trade-off to find for power/cost/life safety 22

  22. Results expected within the next 2-3 years • Improvement given in example plus others should allow a 20% of specific energy (keeping the same life) • Price decrease per kWh will come from better use of materials, process, scale-up • What we can do for battery management simplification and better knowledge of the ageing behaviour will also contribute to cost decrease 22

  23. Thinking 3-6 years ahead 23

  24. Second step: Roadmap towards 250 Wh/kg • Availability of new materials is the key issue: • Nature of materials & type of reaction determine theoretical capacity • Organization (size, nanos or not, conductive additives, coating, blends,, no critical raw source…) helps to go towards theoretical capacity • The gain on one polarity becomes marginal when one polarity has a capacity 4-5 time higher than the other one: both capacities should be increased in an equivalent manner for the best efficiency • The most advanced materials to progress towards the target • Negative materials based on Si & Sn • NMC lithium rich for positive active materials 26

  25. How can we continue to increase specific energy ? 5 5.0V 4 “LiCoPO4” (160mAh/g) 4.9V “Doped LiMn2O4” (100-135 mAh/g) 4.7V 3 “LiMnPO4” (170 mAh/g) 4.2V 2 1 0 0 200 400 600 800 1000 1200 3800 4000 “5V” LiMn2O4&LiMnPO4&LiNMCs Polyanionic compounds (Li1-xVOPO4, LixFePO4) “LiCoO2” TODAY Positive materials “LiNiO2” Vanadium oxides (V2O5, LiV3O8) Potential vs Li/Li+ (V) “MnO2” TOMORROW Li4Ti5O12 Intermetallics d = 4- 8 3D metal oxides Negative materials Nitrides d = 2.1 Phosphides (d  8) Other carbons Si-composites d = 2.3 Graphite Li metal Sn Si Sn-C Capacity (Ah/kg)

  26. Between all Li-metal alloys, Li-Si and Li-Sn are the more interesting … Li1.7Si  Li2.3Si  Li3.2Si  Li4.4Si : 4200 mAh/g Volume changes :  120% for Li1.7Si  160% for Li2.3Si  240% for Li3.2Si  320% for Li4.4Si Volumes changes of carbon around 12 % Li4.4Si, 1000 mAh/g, volume change : 280% • Challenge: find a mean to contain LixMy volume changes on charge / discharge and to improve consecutive capacity loss on cycling : • Nano-sized particles & Electrode structuration ; • Limit the insertion in the case of Si : Li1.7Si (1600 mAh/g).

  27. New negatives: solving the poor cycle life issue • Si or Sn swell during lithium insertion (charge) • Consequence is materials desagregation, conductivity loss, and need to reform passivation layer at each cycle • Research programs everywhere in the world propose possible solutions CHARGE DISCHARGE

  28. Solutions envisaged • Only partial use of materials capacity (less swelling) • Nano structures to contain silicon • Additives for stabilisation • Matsushita announces the first 18650 cell at 3.6 Ah with silicon negative (end 2012) • Life should not be more than 200-300 cycles • Still very insufficient for cycling industrial applications, but substantial • No safety data 28

  29. On the positive side: what’s new ? • New high capacity and high voltage NMC: • Overlithiated materials • Containing two different phases: Li2MnO3 and Li(NixMnyCozO2) • Must be charged at 4,6 V vs Li minimum for activation • Critical point today in terms of electrolyte • Objective: 230 mAh/g (+25%). Not ready industrially • Other families of polyanionic compounds could also be interesting if voltage is sufficient: sulfates, borates… 29

  30. Beyond Li-ion 30

  31. Beyond lithium-ion Lithium air 1000 Wh/kg ?) Negative materials Exchanging more than electron per mole (Mg, Al) Lithium- sulfur 300 Wh/kg ? Use of bio renewable materials Low cost sodium batteries ?

  32. Lithium-sulfur: 300 Wh/kg ? • Advantages • Sulfur is los cost and abundant • High capacity ( exchange 2 electrons) • Limitations and problems • Voltage lower than 3 V • Insulating discharge materials (rapid ageing) • High self-discharge of intermediate discharge compounds in organic media • Risk H2S • Numerous projects running • Polyplus + Sion Power, Oxis Energy : industrial projects • Nanostructured electrodes sulfur/mesoporous carbon(Univ.München) • Task Force of European network Alistore • Research step not finished 32

  33. Conclusion Batteries are key enabling technologies and are on the critical path of many innovations Materials are the core of battery A substantial part of the results on materials has been obtained in the frame of cooperation between materials manufacturers / battery manufacturers, and support of European Commission in many cases As everybody, we have our valley of death: long duration of qualification, cost of demonstrators 33

  34. Thank you for your attention 34

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